The diamagnetic VO2+-iminobenzosemiquinonate anion radical (LIS,H.-.R = H, Me) complexes, (L-)(VO2+)(L-IS(H.-)): (Li)(VO2+) (L-IS(H.-))center dot 3/2MeOH (1 center dot 3/2MeOH), (L-2(-)) (VO2+)) (2), and (L-2(-))(VO2+)(L-IS(Me.-))center dot 1/2L(Me)(AP) (3 center dot 1/2 L-AP(Me)), incorporating tridentate monoanionic NNO-donor litgands {L = L-1(-) or L-2(-), L1H = (2-[(phenylpyridin-2-yl-methylene)amino]phenol; L2H = 1-(2-pyridylazo)-2-naphthol; L-IS(H.-) = o-iminobenzosemiquinonate anion radical; L-IS(Me.-) = o-imino-p-methylbenzosemiquinonate anion radical; and L-AP(Me) = o-amino-p-methylphenol} have been isolated and characterized by elemental analyses, IR, mass, NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1 center dot 3/2MeOH and 3 center dot 1/2 L-AP(Me). Complexes 3 center dot 1/2MeOH, 2, and 3 center dot 1/2L(AP)(Me) absorb strongly in the visible region because of intraligand (IL) and ligand-to-metal charge transfers (LMCT). 1 center dot 3/2MeOH is luminescent (lambda(ext), 333 nm; lambda(em), 522, 553 nm) in frozen dichloromethane-toluene glass at 77 K due to pi(diimine)-pi(diimine)*, transition. The V-O-phenolato (cis to the V=O) lengths, 1.940(2) and 1.984(2) angstrom, respectively, in 1 center dot 3/2MeOH and 3 center dot 1/2 L-AP(Me) are consistent with the VO2+ description. The V-O-iminosemiquinonate (trans to the V=O) lengths, 2.1324(19) in 1 center dot 3/2MeOH and 2.083(2) angstrom in 3 center dot 1/2L(AP)(Me), are expectedly similar to 0.20 angstrom longer due to the trans influence of the V=O bond. Because of the stronger affinity of the paramagnetic VO2+ ion to the L-IS(H.-) or L-IS(Me.-), the V-N-iminosemiquinonate lengths, 1.908(2) and 1.921(2) angstrom, respectively, in 1 center dot 3/2MeOH and 3 center dot 1/2 L-AP(Me), are unexpectedly shorter. Density functional theory (DFT) calculations using B3LYP, B3PW91, and, PBE1PBE functionals on 1 and 2 have established that the closed shell singlet (CSS) solutions (VO3+-amidophenolato (L-AP(R2-)) coordination) of these complexes are unstable with respect to triplet perturbations. But BS (1,1) M-s = 0 (VO2+-iminobenzosemiquinonate anion radical (L-IS(R.-)) coordination) solutions of these species are stable and reproduce the experimental bond parameters well. Spin density distributions of one electron oxidized cations are consistent with the [(L-)(VO2+) (L-IQ(R))](+) descriptions [VO2+-o-iminobenzoquinone (L-IQ(R)) coordination], and one electron reduced anions are consistent with the [(L.2-)(VO3+)(L-AP(R2-))](-) descriptions [VO3+-amidophenolato (L-AP(R2-)) coordination], incorporating the diimine anion radical (L-1(.2-)) or azo anion radical (L-2(3-)). Although, cations and anions are not isolable, but electro-and spectro-electrochemical experiments have shown that 3(+) and 3(-) ons are more stable than 1(+), 2(+) and 1(-), 2(-) ions. In all cases, the reductions occur with simultaneous two electron transfer, may be due to formation of coupled diimine/azo anion radicalVO(2+) species as in [(L.2-)(VO2+)(L-AP(R2-))](2-).